Alkanediol phosphoryl monochlorides



Patented Dec. 1, 1953 UNITED STATES PATENT OFFICE ALKANEDIOL PHGSPHORYLMON CHLORIDES Harry .R. Gamrath'and Roger E. Hatton', St. Louis,

Mo assign'orsto Monsanto Chemical Company, Sit-Louis, M0. a corporationof Delaware NoDrawing. Application March 11, 1950, Serial No. 149,221

Claims. 1

Thisinvention relates toalkanediol phosphoryl monochlor-ides; morespecifically, thisinvention relates to allranediol monochlorides havingthe following general formulawhereinA representsa divalentaliphaticorganic radical having the general formula CnHzu wherein nrepresents a whole number from 1 to '7 inclusive andRi represents analkylradical'containingfrom'i' to G'carbon atoms. Representative of apreferred embodiment of this invention, are those alkanediol phosphorylmonochlorides having the .above described general formula wherein'Arepresents a radical having the for- O mula' stitute a preferredembodiment of this invention,.

may,-therefore; be represented by theformula wherein'R is'select'edfrom'th'e group consisting plasticizers, etc. Neutral ortho-phosphateesters,

forexample, are obtained by reacting thea'lkanediol phosphoryl'monochlorides of this invention with a slight excess of an. alkali metalarylate or with" alcohols. These phosphate. esters have exceptionalutility as plasticizers, functionalv fluids and insecticides; Compoundshaving. exceptional utility as oil additives maybe prepared. by reactingthe 'alkanediol phosphoryl monochlorides of this invention with ammonia,amines.

or mercaptans such as thioalc'ohols or thiophenols. When the alkanediolphosphoryl monochlorides' of this invention are hydrolyzed with water,alkanediol phosphoric acids are formed which find use in the" textileand paper manuiacturing industries.

The alkanediol phosphorylmonochlorides of this invention are mobileliquids with a pungent odor. They are essentiallycolorless-butthe-colors may vary from light yellbwto-purple-brown, depending upon theconditions of preparation and the purity ofthe diOLutilized.

The novel alkanediol phospho-ryl monochlorides of this invention aremost conveniently.- preparedby reacting a lmolecular proportionof analkanediol containing a primary and a secondary hydr-oxyl groupandhaving theformula mo-A-e-al wherein A represents-a divalent organicredi'ca'l' having the formula CnH2n wherein n is a whole number from 1to '7 inclusive and R1 is an alkyl radical containing from 1 to 6 carbonatoms; withapproximately a 1 molecular proportion of phosphorusoxychloride, and-removing the hydrogen chloride gas formedduring a thereaction. In preparing the novel alkanediol 'phosphoryl monochlorideswhich constitute a:

preferred embodiment of: this invention, the alkanediol utilized in theabove process may. be represented by the formula wherein R isselectedfrom the group-consisting. of hydrogen and'alkyl radicalscontaining from 1 to 6 carbon atoms, a-nd'R1-is analhyl--radicalcontaining from 1- to 6 carbon-atoms.

The following examplesare illustrative of the novel alkanedi'olphosphoryl monochlorides of this invention:

EXAMPLE I 2-ethyZ-1,3-hexanediol ph'ospharyl monochlorz'de To aone-liter, round-bottomflask fitted w-ith a stirrer, thermometer,dropping funnel and outlet attached to a drying tube, was charged 230.1g. of phosphorus oxychloride." The dropping funnel was charged with219.3 g. of- 2-ethyl-*1;3- hexanediol. The contents of the flask werecooled with an ice bath and then the glycol was slowly added to thephosphorus oxychloride over a twohour period, while maintaining. a.reaction temperature of about l'0-15 C. After all of the: glycol hadbeen added, the ice bath was removed and the temperature ofthe-reactionmixture allowed to rise to about 25 C. with continuous stirring. Theoutlet of the reaction flask was then connected to a water aspirator andhydrogen chloride gas which formed during the reaction, was removed by?reducing the.' pressure slowlyto 1045 mm: Hga'bsolut'e and maintain- 3ing the temperature at 20-25 C. Substantially complete removal of thehydrogen chloride was obtained in about hours.

An essentially quantitative yield of 2-ethyl-1,3- hexanediol phosphorylmonochloride was obtained having the following properties:

Using the equipment and procedure set forth in Example I,2-methyl-1,3-hexanediol phosphoryl monochloride was prepared. using 66.1g. of 2-methyl-1,3-hexanediol and '76.7 g. of phosphorus oxychloride.The yield was essentially quantitative.

EXAMPLE III 1,3-hemanediol phosphoryl monochloride In accordance withthe procedure set forth in Example I, 1,3-hexanediol phosphorylmonochloride was prepared in a quantitative yield, utilizing 118.2 g. of1,3-hexanediol and 153.4 g. of phosphorus oxychloride.

EXAMPLE IV 1,3-butanediol phosphoryl monochloride Utilizing theequipment described in Example I, the reactor was charged with 383.5 g.of phosphorus oxychloride. The dropping funnel was charged with 225.3 g.of 1,3-butanediol. The contents of the reaction flask were cooled withan ice bath and the 1,3-butanediol slowly added to the stirredphosphorus oxychloride over a period of 2 hours, while maintaining areaction temperature of about 10-15 C. After all of the 1,3- butanediolhad been added, the ice bath was removed and the temperature of thereaction mixture allowed to rise to about 25 C. with continuousstirring. Hydrogen chloride gas which formed during the reaction wasremoved by slowr Specific gravity at 25/25 C 1.3675 Crystallizing pointbelow 20 C. Color essentially colorless Chlorine,

Analysis percent Calculated for C4HEO3PC1 20. 82 Found"... 20.94

EXAMPLE V 2-methyZ-1,3-butanediol phosphoryl monochloride In accordancewith the procedure described in Example I, an essentially quantitativeyield of 4 2-methy1-1,3-butanedio1 phosphoryl monochloride was obtained,utilizing as the reactants 104.1 g. of 2-methyl-1,3-butanediol and 153.4g. of phosphorus oxychloride.

Other compounds which are included Within the scope of this invention,and which may be prepared in accordance with the procedure set forth inthe preceding examples, are contained in the following list, which listis to be considered as illustrative rather than limitative of the scopeof this invention:

2-isopropyl-1,3-butanediol phosphoryl monochloride Z-butyI-LS-butanediolphosphoryl monochloride 2-pentyl-1,3-butanediol phosphoryl monochloride2-n-hexyl-1,3-butanediol phosphoryl monochloride 2-(2-methylpentyl) 1,3butanediol phosphoryl monochloride 1,3-pentanediol phosphorylmonochloride 2-ethyl-l,3-pentanediol phosphoryl monochloride2-propy1-1,3-pentanediol phosphoryl monochloride 2-buty1-1,3-pentanediolphosphoryl monochloride 2-isobutyl-1,3-pentanediol phosphorylmonochloride 2-penty1-1,3-pentanediol phosphoryl monochloride2-butyl-1,3-hexanediol phosphoryl monochloride 2-isoamyl-1,3hexanediolphosphoryl monochloride 2-n-hexyl-1,3-hexanediol phosphoryl monochloride1,3-heptanedio1 phosphoryl monochloride 2-ethyl-1,3 -heptanediolphosphoryl monochloride 2-isopropyl 1,3 heptanediol phosphorylmonochloride Z-propyl-LB-heptanediol phosphoryl monochloride2-butyl-1,3-heptanedio1 phosphoryl monochloride 2-pentyl-1,3-heptanediolphosphoryl monochloride 1,3-octanedio1 phosphoryl monochloride2-methyl-1,3-octanediol phosphoryl monochloride 2-ethyl-1,3-octanediolphosphoryl monochloride 2-isopropyl-1,3-octanediol phosphorylmonochloride 2-isobutyl-l,3-octanedio1 phosphoryl monochloride2-pentyl-1,3-octanediol phosphoryl monochloride 1,3-nonanediolphosphoryl monochloride 2-methyl-1,3-nonanediol phosphoryl monochloride2-ethyl-1,3-nonanedio1 phosphoryl monochloride 2-propyl-1,3-nonanediolphosphoryl monochloride 2-butyl-1,3-nonanediol phosphoryl monochloride2-pentyl-1,3 -nonanediol phosphoryl monochloride 2-hexyl-1,3-nonanediolphosphoryl monochloride 4-methyl-1,3-pentanediol phosphoryl monochloride2-methyl 4 methyl-1,3-pentanediol phosphoryl monochloride 2 butyl 4methyl-1,3-pentaned1ol phosphoryl monochloride 4-methyl-L3-hexanediolphosphoryl monochloride 2-methyl 4 ethyl 1,3 hexanediol phosphorylmonochloride I 2-propyl-4,5-dimethyl-1,3-hexanediol phosphorylmonochloride 2-pentyl-4-ethyl-5-methyl-1,3-hexanediol phosphorylmonochloride l m r accuses fi-rethyl-1,3=heptanediol phosphory1monochlorid'e 32?ethyle dimethyl LQ-heptanedibl phosphoryl monochloride'2 butyl 4-ethyl-l,3-heptanediol phos-phoryl mom O'Chlbrid'234,5-triniethyl-1,3-heptanediol phosphoryl monochloride v6=methyl-1,3-heptanediol phosphoryl monochloride6--methyl-I,3"-octanediol phosphorylmonochloride 1 2- propy1i- 4 methyle 1 ,3 octanedi'olphosphoryl monochl'oride lAepentanediolphosphorylmonochloride '3 methyl-L4-hexanediol, phosphoryl" monochloride 2 'ethyl5 =methyl 1,4 heptanediot phosphoryl The procedure set forth in thepreceding examplesfor the preparation of the novel com- .poundsjof thisinvention is subject to substantial variation. "For example, whileapproximately equimolecular proportions of thereactants are preferred, aslight excess of either material may .be utilized. Since the reactionbetween the11alkanediol. and phosphorus oxychloride isessentially-ajquantitative reaction, the utilization: of approximatelyequimolecular proportions-of :the

reactants; results imthe formation of such asubstantially purealkanediol phosphoryl; monochloride. that further purificationtisusually: unnecessary. The temperature maintained during the reaction mayalso be varied over a substantial range, although low temperatures arepreferred. Preferably, the temperature of the reaction mixture ismaintained in the range of from about 0 C. to about 25 C. Temperaturesas high as 50 C. may, however, be utilized and are particularlyadvantageous towards the end of the reaction to facilitate the removalof the hydrogen chloride formed. The hydrogen chloride formed during thereaction may be removed by any method well known to those skilled in theart, such as, by blowing the mixture with air or by placing the reactionmixture under reduced pressure, the latter method being preferable.

In order to obtain the best possible yield and the highest degree ofpurity of the alkanediol phosphoryl monochloride, the reaction may beforced to completion by removing the hydrogen chloride formed, such asby placing the reaction system under reduced pressure, until thereaction mixture analyzes essentially 1 gram-atom chlorine for each molof phosphorus oxychloride charged. In many instances, when thealkanediol phosphoryl monochloride is to be utilized for the preparationof other organic compounds, it is not necessary that the last traces ofthe hydrogen chloride formed in the reaction be removed. Thus, forexample, when the alk-anediol phosphoryl monochloride is to be utilizedfor the preparation of a neutral phosphate ester, it has been found thatwhen the reaction product analyzes about 1.1 gram-atoms of chlorine forevery mol of phosphorus oxychloride charged, the mass is of sumcientpurity for use in the preparation of the neutral phosphate esters.

"6 *Wlrahistlaimedris:

1. Asm'new chemical icompcunds,z-walkanediol phosphoryl monochlorideshaving the formula -H2G-O5 Q A i -o1 wherein A representsa:divalentaliphatic organic radical havin'g: the general formula .CnHZn whereinnrepresents 'a whole number from. 1 to -'l FiIi'ClUSiVGJ'QJIIdi-i R1",represents: anzalkyl" radical containing: from. I to 6103115011 atoms.

- 2.;AsL- new JGHGIITIGBJI compounds; alkanediol phosphorylmonoclrloride'shaving. the formula Rr qn 1 Cl r HC---0 wherein'R isselected from the group consisting of hydrogen and alkyl radicalscontaining from 1 to 6 carbon atoms andRrrepresents an alkyl radicalcontaining from 1 to 6 carbon atoms.

3. 2-ethyl-1,3-hexanediol phosphoryl monochloride.

" 2 methylel,Behexanediol. phosphoryl" mono 5.l'-,3.-h'exanediol";phosphoryLmonochloride. 1 '61.1,3'-butan'edio1;phosphoryl monochlori'd'e. I .7. Zemethyl-LBbutanediollnphosphoryl i-mon'ochloride;

8. A process for preparingzr.alkanediOLphosphoryl monochlorides havingthe formula wherein A represents a divalent aliphatic organic radicalhaving the formula wherein n represents a whole number from 1 toinclusive and R1 represents an alkyl radical con taining from 1 to 6carbon atoms, which comprises reacting a one molecular proportion of analkanediol having the formula OH on H2(JACR wherein A represents adivalent aliphatic organic radical having the formula CnH2n wherein nrepresents a whole number from 1 to '7 inclusive and R1 represents analkyl radical containing from 1 to 6 carbon atoms, with approximately aone molecular proportion of phosphorus oxychloride.

9. A process for the preparation of alkanediol phosphoryl monochlorideshaving the formula which comprises reacting a one molecular proportionof an alkanediol having the formula wherein R is selected from the groupconsisting of hydrogen and alkyl radicals containing from 1 to 6 carbonatoms and R1 is an alkyl radical containing from 1 to 6 carbon atoms,with approximately a one molecular proportion of phosphorus oxychloride.

10. The process as described in claim 9 wherein the alkanediol is2-ethyl-1,3-hexanedio1.

11. The process as described in claim 9 wherewherein R is selected fromthe group consisting of hydrogen and alkyl radicals containing at least1 and not more than 6 carbon atoms and R1 represents an alkyl radicalcontaining from 1 to 6 carbon atoms, which comprises reactingapproximately a 1 molecular proportion of an alkanediol having theformula OH OH wherein R is selected from the group consisting ofhydrogen and alkyl radicals containing from 1 to 6 carbon atoms and R1is an alkyl radical containing from 1 to 6 carbon atoms, withapproximately a 1 molecular proportion of phosphorus oxychloride, whilemaintaining a temperature in the range of from about 0 C. to about 0.,and while removing the hydrogen chloride formed.

16. The process as described in claim 15 wherein the alkanediol is2-ethyl-L3-hexanediol.

17. The process as described in claim 15 wherein the alkanediol is2-methyl-1,3-hexanediol.

18. The process as described in claim 15 wherein the alkanediol is1,3-hexanediol..

19. The process as described in claim 15 wherein the alkanediol is1,3-butanediol.

20. The process as described in claim 15 wherein the alkanediol is2-methy1-1,3-butanediol.

HARRY R. GAMRA'I'H. ROGER E. HA'I'I'ON.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date Toy Aug. 14, 1945 OTHER REFERENCES

1. AS NEW CHEMICAL COMPOUNDS, ALKANEDIOL PHOSHORYL MONOCHLORIDES HAVING THE FORMULA 